EP2554581B1 - Prepreg, fiber-reinforced composite material, and method for producing prepreg - Google Patents

Prepreg, fiber-reinforced composite material, and method for producing prepreg Download PDF

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Publication number
EP2554581B1
EP2554581B1 EP11762855.2A EP11762855A EP2554581B1 EP 2554581 B1 EP2554581 B1 EP 2554581B1 EP 11762855 A EP11762855 A EP 11762855A EP 2554581 B1 EP2554581 B1 EP 2554581B1
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EP
European Patent Office
Prior art keywords
component
fiber
prepreg
reinforced composite
composite material
Prior art date
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EP11762855.2A
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German (de)
English (en)
French (fr)
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EP2554581A1 (en
EP2554581A4 (en
Inventor
Takayuki Fujiwara
Jun Misumi
Ayumi Matsuda
Kenichi Yoshioka
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Toray Industries Inc
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Toray Industries Inc
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Publication of EP2554581A4 publication Critical patent/EP2554581A4/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/56—Damping, energy absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/009—Additives being defined by their hardness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions

  • the present invention relates to a fiber-reinforced composite material which excels in rigidity, strength, and vibration damping properties, and which are suitable for sports applications and general industrial applications, also relates to a prepreg which is suitably used for production thereof and a method for production thereof.
  • Patent Document 3 discloses a tennis racket made of a fiber-reinforced composite material in which an epoxy resin composition that contains a specific epoxy resin component, epoxy-incompatible rubber particles and polyvinyl formal, is used as matrix resin.
  • an epoxy resin composition that contains a specific epoxy resin component, epoxy-incompatible rubber particles and polyvinyl formal, is used as matrix resin.
  • some rubber particles which are incompatible with epoxy resin enter the interior of reinforcing fiber bundles and the other rubber particles are filtered, with the result that a larger quantity of rubber component exists on the surface of the prepreg than in its interior. Consequently, subsequent to lamination, a large quantity of rubber component can exist between prepreg layers.
  • the microscope to be used may be either an optical microscope or a scanning electron microscope. It is advisable to use either of them depending on particle size and the staining method used.
  • the ratio of particles localized near the prepreg surfaces is measured on the basis of area ratio. However, this procedure is substantially equivalent to measuring the mass ratio, since the mass ratio of particles is equal to their area ratio.
  • tetraglycidyl diaminodiphenyl methane examples include "SUMIEPOXY (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.); YH434L (manufactured by Nippon Steel Chemical Co., Ltd.); “jER (registered trademark)” 604 (manufactured by Mitsubishi Chemical Corporation); and “ARALDITE (registered trademark)” MY720 and MY721 (these products are manufactured by Huntsman Advanced Materials Co., Ltd.).
  • SUMIEPOXY registered trademark
  • ELM434 manufactured by Sumitomo Chemical Co., Ltd.
  • YH434L manufactured by Nippon Steel Chemical Co., Ltd.
  • jER registered trademark
  • 604 manufactured by Mitsubishi Chemical Corporation
  • ARALDITE registered trademark
  • cresol novolac type epoxy resin examples include "EPICLON (registered trademark)" N-660, N-665, N-670, N-673 and N-695 (these products are manufactured by DIC Corporation); EOCN-1020, EOCN-102S, and EOCN-104S (these products are manufactured by Nippon Kayaku Co., Ltd.)
  • an epoxy resin having an epoxy equivalent of 800 - 5,500 is preferred because it increases the adhesiveness to urethane particles, thereby providing excellent vibration damping properties. More preferable is an epoxy resin having an epoxy equivalent of 800 - 2,500. If the epoxy equivalent is lower than 800, the adhesiveness improvement effect will not be sufficient. If the epoxy equivalent is higher than 5,500, the viscosity of the epoxy resin composition obtained will be too high, possibly making it difficult to produce a prepreg.
  • a bisphenol type epoxy resin having an epoxy equivalent of 800 - 5,500 is more preferable in terms of the balance between the vibration damping properties and the toughness. Still more preferable are bisphenol A type epoxy resin and a bisphenol F type epoxy resin having an epoxy equivalent of 800 - 5,500.
  • Examples of commercial products dicyandiamide include DICKY-7 and DICY-15 (these products are manufactured by Mitsubishi Chemical Corporation).
  • the active hydrogen group accounts for more than 1.0 equivalent, the cured resin will decrease in plastic deformation capacity, although it may have a sufficiently high reaction rate, glass transition temperature, and modulus. Accordingly, the fiber-reinforced composite material may have poor shock resistance.
  • those carbon fibers whose tensile modulus is 230 - 450 GPa are preferable, since not only can a light-weight and high-rigidity fiber-reinforced composite material be obtained, but also good vibration damping properties can be achieved. If the tensile modulus is less than 230 GPa, the rigidity and the vibration damping properties of the fiber-reinforced composite material obtained tend to decrease. Furthermore, if the tensile modulus exceeds 450 GPa, the adhesion properties are liable to be reduced and the strength may decrease, although energy conversion caused by the friction heat between carbon fibers and epoxy resin can work to improve the vibration damping properties of the fiber-reinforced composite material. In view of the balance between the dynamic properties and the vibration damping properties of the resulting fiber-reinforced composite material, carbon fibers with a tensile modulus of 230 - 300 GP are more preferably used.
  • the prepreg precursor obtained by impregnating component (C) with component (B) has a reinforcing fiber density per unit area of 50 - 200 g/m 2 . If the quantity of reinforcing fibers is 50 g/m 2 or less, it is necessary to increase the number of layers laminated, in order to achieve a predetermined thickness when molding the fiber-reinforced material, possibly requiring complicated operations. If the quantity of reinforcing fibers exceeds 200 g/m 2 , on the other hand, the draping quality of the resulting prepreg tends to be poor. Furthermore, the fiber's mass content is preferably 60 - 90% by mass, more preferably 65 - 85% by mass, and still more preferably 70 - 80% by mass.
  • component (E) is incompatible with the third epoxy resin composition
  • the glass transition temperature that is determined from a storage modulus curve based on dynamic viscoelasticity measurements of a cured resin composition consisting of component (E) and the third epoxy resin composition. That is, dynamic viscoelasticity measurements are used to determine the glass transition temperatures of the following items: a cured resin composition obtained by curing a resin composition consisting of component (E) and the third epoxy resin composition; a plate-like molded product formed only of component (E); and a cured resin obtained by curing the third epoxy resin composition only.
  • tan ⁇ of component (E) at 10°C is 0.15 or more, more preferably 0.2 or more. If tan ⁇ is lower than 0.15, vibration damping properties are not sufficient.
  • tan ⁇ at 10°C can be determined by subjecting the plate-like cured resin composition prepared by the method mentioned above to dynamic viscoelasticity measurement by the method mentioned above.
  • the degree of localization of particles in the fiber-reinforced material can be evaluated as follows. First, a cross section of a fiber-reinforced material is photographed at a magnification of 200 or more (see FIG. 5 or FIG. 6 ). In this photograph, an averaged borderline (4) is drawn between a layer comprising components (F) and (G) and a layer where component (G) is not present.
  • the averaged borderline is drawing as follows. First, five or more points are selected on a borderline between a layer comprising components (F) and (G) and a layer where component (G) is not present.
  • the region located between the two averaged borderlines on either side of said layer is defined as an interlayer region.
  • the sum of the cross-sectional areas of the particles present in an interlayer region is determined.
  • a region extending from the averaged center thickness line (5) of a layer which comprises components (F) and (G) and which is adjacent to a layer free from component (G) to the averaged center thickness line (5) of another layer which comprises components (F) and (G) and which is located on the other side of and adjacent to said layer free from component (G) is defmed as the entire region to be covered by the measurement of the cross-sectional areas of particles.
  • the sum of the cross-sectional areas of all particles present in this entire region is determined.
  • the microscope to be used may be either an optical microscope or a scanning electron microscope. It is advisable to use either of them depending on particle size and the staining method used.
  • the ratio of particles present in an interlayer region is measured on the basis of area ratio. However, this procedure is substantially equivalent to measuring the mass ratio, since the mass ratio of particles is equal to their area ratio.
  • Reinforcing fiber is used as component (G). Examples of the reinforcing fiber given for component (C) can also be used here.
  • the fiber-reinforced composite material of the present invention further contains component (H), and that component (E) is contained in component (H).
  • Component (H) is a cured resin of a fourth epoxy resin composition which is not compatible with component (E). Maintaining component (E) in the state of being contained in component (H) makes it possible to prevent voids from being formed during the laminating and curing steps for producing the fiber-reinforced composite material.
  • the method to be used for producing the fiber reinforced composite material of the present invention is not subject to particular restrictions, but useful ones include the prepreg lamination molding method, the resin transfer molding method, the resin film infusion method, the hand layup method, the sheet molding compound method, the filament winding method, and the pultrusion method.
  • the prepreg lamination molding method which uses a prepreg of said present invention, is preferable, since said method can produce fiber reinforced composite materials with higher rigidity and strength.
  • a prepreg is laminated on a tool plate having a predetermined shape and coated with a bagging film, followed by curing it by heating under pressure while deaerating the interior of a laminated product.
  • the autoclave molding method can precisely control the fiber orientation and does not suffer from significant void formation, allowing high-quality moldings with good dynamic/static properties to be produced.
  • a prepreg is wound around a core bar such as mandrel to produce a tubular body of a reinforced composite material.
  • the wrapping tape method is suitable to produce rod-like bodies such as golf club shafts, fishing rods, etc. More specifically, in this method, a prepreg is wound around a mandrel and a wrapping tape formed of a thermoplastic film is wound around the outside of the prepreg for the purpose of fixing the prepreg and applying pressure thereto, followed by heat-curing the resin in an oven and subsequently pulling out the core bar to produce a tubular body.
  • the flexural strength of the fiber-reinforced composite material of the present invention is 90% or more of the flexural strength of a fiber-reinforced composite material which is the same as said fiber-reinforced composite material except that component (E) is not contained.
  • the flexural strength refers to a value converted on the basis of a fiber content of 60% by volume. If the flexural strength is less than 90%, golf club shafts, fishing rods, tennis rackets, etc. produced by molding it will fail to have sufficient strength, or will have an increased weight if improved in strength.
  • components (B) and (D), the third epoxy resin, and the fourth epoxy resin are as follows.
  • a cured resin or a plate-like molding was cut with a diamond cutter to a size 13 mm wide and 35 mm long.
  • a dynamic viscoelasticity measuring device (DMAQ800: Manufactured by TA Instruments, Inc.) was used to heat such a sample to -70°C to 250°C at a temperature rise rate of 5°C/min. Then measurements of the storage modulus and tan ⁇ were made in a bending mode with a frequency of 1.0 Hz. The onset temperature of the storage modulus at this time was taken as the glass transition temperature
  • a unidirectional prepreg was produced by the same procedure as in Example 2 except that (A-1) was used as component (A) and added to a content of 7% by mass. Results are given in Table 5. The surface localization rate was a satisfactory 99%. Next, a fiber-reinforced composite material was prepared by the same procedure as in Example 1. Results are given in Table 5. The interlayer localization rate was a satisfactory 95%. The loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 162%, 93%, 99%, and 100%, respectively, as compared with Comparative Example 1. Tg was also satisfactory. The loss factor rose greatly as compared with Example 1.
  • a unidirectional prepreg precursor and a fiber-reinforced comparative material were produced by the same procedure as in Comparative Example 1 except that component (B) was replaced with the resin composition of Reference Example 3. Results are given in Table 8. Being low in loss factor, the material was not acceptable.
  • a unidirectional prepreg was produced by the same procedure as in Example 1 except that component (B) was replaced with the resin composition of Reference Example 3.
  • the surface localization rate was a satisfactory 99%.
  • a fiber-reinforced composite material was prepared by the same procedure as in Example 1.
  • the interlayer localization rate was a satisfactory 97%.
  • the loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 140%, 98%, 96%, and 100%, respectively, which were better as compared with Comparative Example 3, and the flexural strength was slightly improved as compared with Example 1 by using 1.0 equivalent of the curing agent. Tg was also satisfactory.
  • a unidirectional prepreg was produced by the same procedure as in Example 1 except that component (B) was replaced with the resin composition of Reference Example 6.
  • the surface localization rate was a satisfactory 98%.
  • a fiber-reinforced composite material was prepared by the same procedure as in Example 1. Results are given in Table 5.
  • the interlayer localization rate was a satisfactory 96%.
  • the loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 136%, 99%, 104%, and 99%, respectively, which were better as compared with Comparative Example 7.
  • Tg increased greatly as compared with Example 1 as a result of using dicyclopentadiene type epoxy resin as the epoxy resin in component (B).
  • a unidirectional prepreg was produced by the same procedure as in Example 1 except that component (B) was replaced with the resin composition of Reference Example 9.
  • the surface localization rate was a satisfactory 99%.
  • a fiber-reinforced composite material was prepared by the same procedure as in Example 1. Results are given in Table 6.
  • the interlayer localization rate was a satisfactory 96%.
  • the loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 141 %, 97%, 99%, and 101%, respectively, which were better as compared with Comparative Example 10.
  • Tg increased as compared with Example 1 as a result of using isocyanate-modified epoxy resin as the epoxy resin of component (B).
  • a unidirectional prepreg precursor and a fiber-reinforced comparative material were produced by the same procedure as in Comparative Example 1 except that component (B) was replaced with the resin composition of Reference Example 10. Results are given in Table 9. Being low in loss factor, the material was not acceptable.
  • a unidirectional prepreg precursor and a fiber-reinforced comparative material were produced by the same procedure as in Comparative Example 1 except that component (B) was replaced with the resin composition of Reference Example 12. Results are given in Table 9. Being low in loss factor, the material was not acceptable.
  • a unidirectional prepreg was produced by the same procedure as in Example 1 except that component (B) was replaced with the resin composition of Reference Example 13.
  • the surface localization rate was a satisfactory 99%.
  • a fiber-reinforced composite material was prepared by the same procedure as in Example 1. Results are given in Table 6.
  • the interlayer localization rate was a satisfactory 96%.
  • the loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 138%, 99%, 103%, and 99%, respectively, which were better as compared with Comparative Example 13. Tg was also satisfactory.
  • a unidirectional prepreg was produced by the same procedure as in Example 1 except that component (B) was replaced with the resin composition of Reference Example 15.
  • the surface localization rate was a satisfactory 98%.
  • a fiber-reinforced composite material was prepared by the same procedure as in Example 1. Results are given in Table 6.
  • the interlayer localization rate was a satisfactory 97%.
  • the loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 137%, 98%, 96%, and 100%, respectively, which were better as compared with Comparative Example 15. Tg was also satisfactory.
  • the resin composition of Reference Example 16 and said (A-1) were kneaded by the same procedure as in Reference Example 46 to produce a resin composition. Using a reverse roll coater, this resin composition and the epoxy resin composition of Reference Example 1 were applied separately to pieces of release paper to prepare resin films. In the next place, using the resin film obtained in Reference Example 1, the same procedure as in Comparative Example 1 was carried out to produce a unidirectional prepreg precursor with a fiber mass per unit area of 125 g/m 2 and a fiber content by mass of 76%. The resin composition of Reference Example 16 and the resin film obtained from said (A-1) were stuck to a surface of this unidirectional prepreg precursor by applying a pressure using a heated press roll to produce a unidirectional prepreg.
  • the surface localization rate was a satisfactory 99%. Using this unidirectional prepreg, the same procedure as described in Reference Example 1 was carried out to produce a fiber-reinforced composite material. Results are given in Table 6. The interlayer localization rate was a satisfactory 96%. The loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 138% and 98%, respectively, which were better as compared with Comparative Example 1, and 138%, 98%, 98%, and 100%, respectively, which were better as compared with Comparative Example 16. Tg was also satisfactory.
  • a unidirectional prepreg was produced by the same procedure as in Example 1 except that component (B) was replaced with the resin composition of Reference Example 19.
  • the surface localization rate was a satisfactory 98%.
  • a fiber-reinforced composite material was prepared by the same procedure as in Example 1. Results are given in Table 7.
  • the interlayer localization rate was a satisfactory 97%.
  • the loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 144%, 98%, 93%, and 101%, respectively, which were better as compared with Comparative Example 18.
  • Tg was also satisfactory.
  • the loss factor increased as compared with Example 1 as a result of adding bisphenol A type epoxy resin with an epoxy equivalent of 1930 to the epoxy resin of component (B).
  • Example 25 A unidirectional prepreg was produced by the same procedure as in Example 1 except that component (B) was replaced with the resin composition of Reference Example 20. The surface localization rate was a satisfactory 98%. Next, a fiber-reinforced composite material was prepared by the same procedure as in Example 1. Results are given in Table 7. The interlayer localization rate was a satisfactory 95%. The loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 146%, 99%, 100%, and 100%, respectively, which were better as compared with Comparative Example 19. Tg was also satisfactory. The loss factor increased as compared with Example 1 as a result of adding bisphenol A type epoxy resin with an epoxy equivalent of 4000 to the epoxy resin of component (B).
  • Comparative example 22 A unidirectional prepreg precursor and a fiber-reinforced comparative material were produced by the same procedure as in Comparative Example 1 except that component (B) was replaced with the resin composition of Reference Example 23. Results are given in Table 10. Being low in loss factor, the material was not acceptable.
  • a unidirectional prepreg was produced by the same procedure as in Example 1 except that component (B) was replaced with the resin composition of Reference Example 23.
  • the surface localization rate was a satisfactory 99%.
  • a fiber-reinforced composite material was prepared by the same procedure as in Example 1. Results are given in Table 7.
  • the interlayer localization rate was a satisfactory 97%.
  • the loss factor, 90-degree flexural strength, zero-degree flexural modulus, and zero-degree flexural strength were 146%, 98%, 96%, and 100%, respectively, which were better as compared with Comparative Example 22. Tg was also satisfactory.
  • the loss factor increased as compared with Example 26 as a result of adding bisphenol F type epoxy resin with an epoxy equivalent of 2,270 to the epoxy resin of component (B).
  • Comparative example 23 A unidirectional prepreg precursor and a fiber-reinforced comparative material were produced by the same procedure as in Comparative Example 1 except that component (B) was replaced with the resin composition of Reference Example 24. Results are given in Table 10. Being low in loss factor, the material was not acceptable.

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EP11762855.2A 2010-03-30 2011-03-29 Prepreg, fiber-reinforced composite material, and method for producing prepreg Not-in-force EP2554581B1 (en)

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